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1.
The rotational spectra of six excited vibrational states of dimethylallene were measured and assigned to the corresponding vibrational levels, and for three more excited state spectra at least the rotational constants could be determined. Between the two lowest excited levels of symmetry species b2 and b1 of group C2v a strong a-type Coriolis coupling was found to exist. The evaluation of the resulting perturbation by a diagonalization of the energy matrix yielded ζ(a) = 0.36 and a precise value for the vibrational energy difference 48.761 GHz (1.6 cm?1). The state b2 is believed to be the first excited torsional substate (01, 10)1 of methyl internal rotation, and the rotational transitions of this state as well as those of the strongly coupled state b1 presented very irregular multiplet splittings. On the other hand, the splittings of the next-higher excited state of species a2 which could be identified as the partner torsional substate (01, 10)2, followed the regular pattern, yielding an internal rotation barrier V3 (2079 cal/mole) not unlike that derived earlier from ground state splittings.  相似文献   

2.
The high-resolution microwave spectrum of the axial conformer of cyclohexyl chloride has been assigned for both the Cl(35) and Cl(37) isotopic species, in natural abundance. Moreover, the high-resolution microwave spectrum of the equatorial conformer, previously assigned in the ground state [Chem. Phys. Lett.21, 592–594 (1973)], has been further investigated. Several low-energy vibrational satellites have been studied for the Cl(35) isotopic species of both the axial and the equatorial isomers. The ground state centrifugal distortion constants for both the isotopic species of the two rotamers, and the quadrupole coupling constants of Cl(35) and Cl(37) axial isomer and of Cl(37) equatorial isomer (not reported previously) have been determined. From line relative intensity measurements the energy difference between the two conformers has been calculated to be 0.51 ± 0.15 kcal/mol, the equatorial isomer being more stable. In the same way, the vibrational energies of the investigated vibrational satellites have been computed. A structural model for axial cyclohexyl chloride is proposed on the basis of the available experimental data.  相似文献   

3.
The microwave “a” and “c” type spectra of four isotopic species of CH3NHCl in the ground state and of CH3NHCl35 and CH3NDCl35 in the first excited torsional state have been analyzed. From the A-E torsional splittings of the excited state the torsional barrier height has been determined to be V3 = 3710 ± 46 cal/mole. The “c” type transitions show an inversion doubling of 4.60 ± 0.10 MHz in the ground state and of 5.25 ± 0.10 MHz in the first excited torsional state. Such doublings are independent on the rotational quantum numbers within the experimental errors. The height of the inversion barrier has been roughly evaluated by using the Dennison-Uhlenbeck potential.  相似文献   

4.
Rotational transitions of the μa and μb type have been identified with microwave-microwave double resonance measurements for 1-chloro-2-butyne in the ground vibrational state. In the first excited state of the methyl torsion only μa-type transitions have been identified. The A-type transitions of the ground vibrational state can be described perfectly by the rigid rotor approximation with centrifugal corrections. Using the internal axis method the barrier to internal rotation was determined from the A,E splittings: V3 = 10.05 ± 0.09 cm−1. A model which allowed for geometry relaxation upon internal rotation was used to fit one set of parameters to the transition frequencies of both ground state and first excited torsional state. The sixfold contribution to the barrier was found to be negligible: V6 = −0.4 ± 0.3 cm−1.  相似文献   

5.
The microwave spectrum of 2-chloropyridine, C5H4NCl, has been studied in the frequency range from 26.5–40.0 GHz. The spectrum is characterized by strong parallel type transitions of a near-prolate asymmetric top. The assigned transitions have been used to evaluate the ground state rotational constants of the two chlorine isotopes. The rotational constants are (in MHz): A = 5872.52, B = 1637.83, C = 1280.48 for the 35Cl isotopic species and A = 5872.16, B = 1591.76, C = 1252.17 for the 37Cl isotopic species. The small inertial defect indicates the molecule is planar. In addition an excited vibrational state of C5H4N35Cl has been observed and analyzed. The chlorine quadrupolar coupling constants were determined for the ground state and are: χaa = ?71.9 MHz for 35Cl and χaa = ?54.9 MHz for 37Cl. By assuming the pyridine ring structure the CCl bond length is found to be 1.72 Å.  相似文献   

6.
Microwave spectra have been measured for four isotopically substituted species of hypochlorous acid (D16O35Cl, D16O37Cl, H18O35Cl, H18O37Cl). Both a- and b-type transitions have been analyzed for rotational, centrifugal distortion, and Cl nuclear quadrupole coupling constants. The distortion constants, together with vibrational wavenumbers, have been used to evaluate a valence harmonic force field. Effective, substitution, ground state average, and estimated equilibrium structures are presented.  相似文献   

7.
The microwave spectrum of ethylcyanide-d5 has been recorded from 18.0 to 40.0 GHz. Both a-type and b-type transitions were observed and assigned. Also, the R-branch assignments have been made for three excited states of the internal torsional mode and two excited states of the CN inplane bending mode as well as an excited vibrational state involving both of these motions. The barrier to internal rotation was determined to be 3.00 ± 0.15 kcal/mole from the E, A splittings of the third excited state. The quadrupole coupling constants of the14N nucleus were found to have values of ?3.213, 1.168, and 2.045 MHz for χaa, χbb, and χcc, respectively. These results are compared to those previously obtained on the corresponding hydrogen compound.  相似文献   

8.
The ground vibrational state microwave spectrum of CHD2Cl has been studied in the region 26.5–40.0 GHz. From the observation of weak c-type transitions the A0 rotational constants of CHD235Cl and CHD237Cl have been determined to be 95 426.08 ± 0.06 and 95 425.23 ± 0.11 MHz, respectively. The observed a-type and c-type transitions have been used to obtain A, B, C, all five quartic and one sextic distortion constants present in the reduced Hamiltonian of Watson for the 35Cl and 37Cl isotopic modifications of CHD2Cl.  相似文献   

9.
The rotational spectra of eight isotopomers of 1-chloro-1-fluoroethylene in the 6-22 GHz region have been collected and analyzed. Each rotational transition is split into hyperfine components by the chlorine (either 35Cl or 37Cl) nuclear quadrupole coupling interaction and additionally, one or more smaller interactions such as the spin-rotation interaction due to the fluorine atom, hydrogen-hydrogen spin-spin coupling interactions, and in appropriately substituted species, the deuterium nuclear quadrupole hyperfine interaction. The rotational constants derived from these isotopomers allow the determination of average and Kraitchman substitution structures for 1-chloro-1-fluoroethylene, whereas the availability of the diagonal chlorine nuclear quadrupole coupling constants for all the isotopomers provides complete quadrupole coupling tensors for both 35Cl and 37Cl. In the course of this work, the rotational spectrum of an excited vibrational state of the normal isotopomer was observed, which ab initio calculations suggest should be assigned to ν9=1, an in-plane bending motion at the CFCl end of the molecule.  相似文献   

10.
The microwave spectrum of 1-cyanocyclohexene has been investigated in the frequency regions 8–12.4 and 18–26.5 GHz. A-Type transitions in the ground state and three excited states have been assigned. The rotational constants in the ground state were determined to be A = 4565.98 ± 0.46, B = 1423.44 ± 0.01, and C = 1136.17 ± 0.01 MHz. From the experimental data, it was suggested that the molecule has an equilibrium half-chair conformation similar to those of cyclohexene and 1-fluorocyclohexene. From the hyperfine splittings of the 14N nucleus, the quadrupole coupling constant, Xaa, was found to be 4.2 MHz.  相似文献   

11.
The millimeterwave rotational spectrum of o-chlorotoluene is investigated in the frequency region 150-250 GHz. Many rotational lines show splitting due to internal rotation of the methyl group. The analysis of the internal rotation splitting allows us to determine with precision the potential barrier to internal rotation of the methyl group. However, it is found that the moment of inertia of the methyl top is probably much smaller than usually assumed, which significantly affects the value of the barrier. Accurate centrifugal distortion constants are obtained for the ground states of 35Cl and 37Cl isotopologues as well as for an excited vibrational state.  相似文献   

12.
Millimeter wave rotational spectra of phosphorus oxychloride (OPCl3) in the ground and excited vibrational states have been recorded and analyzed. The v5 = 1 and v6 = 1 state spectra show large splittings due to l resonance and the effect of the 2, -1 term rt. Coriolis constants have been obtained for the two lowest degenerate states. The spectra of the asymmetric top species OP35Cl237Cl have been analyzed and centrifugal distortion constants obtained. These have been used to determine the harmonic force field of the molecule.  相似文献   

13.
The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm?1 above the ground state.and the next higher state is roughly 200 cm?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μa| = 2.88 ± 0.03 D, |μb| = 1.23 ± 0.04 D and |μc| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.  相似文献   

14.
The microwave spectrum of fluoroacetyl chloride has been studied in the 8–40 GHz region and transitions arising from one conformer have been assigned. This conformer has all the heavy atoms in a plane with the fluorine and chlorine atoms trans to one another. The rotational constants and nuclear quadrupole coupling constants for the ground vibrational state are (in MHz): H2FCCO35Cl: A = 9025.82, B = 2403.92, C = 1920.70, χaa = ?47.7, χbb = 23,7, χcc = 24.1; H2FCCO37Cl: A = 8994.95, B = 2342.24, C = 1879.75, χaa = ?38.0, χbb = 18.9, χcc = 19.1. The spectrum of the first excited torsional state has been assigned. Some lines possibly due to a second conformer have been observed but not yet assigned.  相似文献   

15.
The infrared active ν7 and ν5 fundamentals of disilane, coupled by an x,y Coriolis interaction, have been analysed on a Fourier transform spectrum between 2120 and 2225?cm?1, at the Doppler limited spectral resolution. A Fermi resonance with 2ν 2?+?ν9 affects the Δ K?=?1 side of ν7, and both ν7 and ν5 show the effects of several additional localized perturbations. Line splittings in the ν5 transitions are not observed, showing that the torsional splitting in the ν5 excited state and in the vibrational ground state are almost equal. The intrinsic torsional splitting of ν7 is found to be smaller than in the ground vibrational state by 0.0085?cm?1. This splitting value and those found for the other two infrared active degenerate fundamentals, ν8 and ν9, follow the trend expected from our theoretical predictions. Exploratory numerical calculations show that the decrease of the torsional splittings, observed in the fundamental degenerate vibrational states of disilane, can actually be accounted for by the head–tail and torsional Coriolis coupling of all the degenerate vibrational fundamentals, in several torsional states.  相似文献   

16.
A chirped pulse microwave spectrometer has been used to record microwave spectra of the 35Cl and 37Cl isotopologues of methyl chlorodifluoroacetate, CClF2C(O)OCH3, between 8 GHz and 16 GHz. The target compound was spectroscopically examined as it participated in a supersonic expansion of argon. Only one conformer was observed. The rotational spectra were recorded with sufficient resolution to observe (i) splittings due to the internal rotation of the methyl group, and (ii) splittings from the coupling of the chlorine quadrupolar nucleus. A total of 785 transitions have had quantum numbers assigned. Analysis of the spectra observed has produced an experimental barrier to the methyl group internal rotation, V3, of 370(2) cm−1. It is noted that this barrier is a little lower than that determined for methyl acetate [V3 = 425 cm−1, J. Sheridan, W. Bossert and A. Bauder, J. Mol. Spectrosc., 80 (1980) 1-11], and this is rationalized through a comparison of molecular structures. Lastly, all components of both the 35Cl and 37Cl chlorine nuclear electric quadrupolar coupling tensor have been determined.  相似文献   

17.
The microwave spectrum of 35Cl and 37Cl species of chloroiodomethane was investigated in the frequency region of 9–35 GHz. The b-type R-branch and Q-branch transitions were assigned. The rotational constants of the ground state were determined to be A = 27 418.81 ± 0.10, B = 1621.879 ± 0.024, and C = 1545.730 ± 0.044 MHz for the 35Cl species; and A = 27 261.46 ± 0.16, B = 1562.240 ± 0.047, and C = 1491.008 ± 0.092 MHz for the 37Cl species. From the hyperfine splitting of the I, 35Cl, and 37Cl nuclei, the nuclear quadrupole coupling constants were determined to be χaa = −1404.5 ± 3.8, χbb = 383.4 ± 2.1, χcc = 1021.1 ± 4.3, and ∥χab∥ = 1176.5 ± 3.6 MHz of iodine; χaa = −26.8 ± 2.3, χbb = −11.0 ± 1.2, and χcc = 37.8 ± 2.6 MHz of 35Cl for the 35Cl species; χaa = −1423.2 ± 5.5, χbb = 389.1 ± 2.9, χcc = 1034.1 ± 6.2, and ∥χab∥ = 1170.2 ± 6.9 MHz of iodine; and χaa = −20.4 ± 3.3, χbb = −9.1 ± 1.8, and χcc = 29.5 ± 3.7 MHz of 37Cl for the 37Cl species, respectively. The centrifugal distortion constants were also determined using all of the assigned transitions. A brief discussion of the procedure for analyzing the quadrupole hyperfine structures of a molecule containing two quadrupolar nuclei is also provided.  相似文献   

18.
Rotational spectra have been recorded for both the 35Cl and 37Cl isotopic forms of two structural conformations of 2-chloroethyl ethyl sulfide (CEES). The rotational constants of the 35Cl and 37Cl isotopomers were used to identify the conformational isomers. A total of 236 hyperfine transitions have been assigned for 47 rotational transitions of the 35Cl isotope of a GGT conformer, and 146 hyperfine have been assigned for 37 rotational transitions of the 37Cl isotopomer. For the second conformer, a total of 128 (110) hyperfine and 30 (28) rotational transitions have also been assigned to the 35Cl (37Cl) isotopes of a TGT conformation. The extensive hyperfine splitting data, measured to high resolution with a compact Fourier transform microwave spectrometer, were used to determine both the diagonal and off-diagonal elements of the 35Cl and 37Cl nuclear quadrupole coupling tensors in the inertial tensor principal axis system. The experimental rotational constant data, as well as the 35Cl and 37Cl nuclear quadrupole coupling tensors, were compared to the results from 27 optimized ab initio (HF/6-311++G∗∗ and MP2/6-311++G∗∗) model structures.  相似文献   

19.
The splittings due to the three chlorine quadrupoles, observed in the millimeter-wave rotational spectra of Si35Cl3H in the ground and ν6 = 1 excited vibrational states, have been analyzed and the quadrupole parameters determined. In particular, splittings observed for the kl − 1 = −1 lines in ν6 = 1 are explained in terms of the asymmetry parameter ηQ. The value obtained is consistent with the electric field gradient at the 35Cl nuclei having cylindrical symmetry about the SiCl bond.  相似文献   

20.
The far-infrared spectrum of methyl amine has been studied in the region 40 to 350 cm−1 by Fourier transform spectroscopy with an apodized resolution of 0.005 cm−1 or better. Both the pure rotational spectrum and the spectrum of the fundamental torsional band have been assigned. This paper reports the ground state constants obtained from a global fitting of a data set including ground state microwave transitions from the literature, as well as far-infrared pure rotational ground state transitions and ground state combination differences from the torsional band obtained in this work. Slightly over 1000 energy differences for the ground state with 0 ≦ K ≦ 19 and KJ ≦ 30 were fit to 30 molecular parameters from a group theoretical formalism developed earlier, and a standard deviation of ±0.00063 cm−1 was obtained. An ambiguity (noted earlier in the microwave literature) in the determination of the structural parameter ϱ, which arises when two large amplitude motions are present in the molecule, can be understood and resolved using the present formalism.  相似文献   

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